Amino acid copolymers having pendent polysaccharide moieties and uses thereof

ABSTRACT

A water-soluble or water-dispersible amino acid copolymer having pendent polysaccharide moieties. The invention also provides a method for cleaning an article and a method of providing soil resistance to an article using the amino acid copolymer having pendent polysaccharide moieties. The amino acid copolymers are useful in cleaning compositions such as laundry detergents, dishwashing detergents, prespotters, fabric softeners, and hard surface cleaners.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of U.S. patent application Ser. No. 09/218,584,filed Dec. 22, 1998, now U.S. Pat. No. 5,962,400.

FIELD OF THE INVENTION

The present invention relates to water-soluble or water-dispersibleamino acid copolymers having pendent polysaccharide moieties. Theinvention also provides a method for cleaning an article and a method ofproviding soil resistance to an article using the amino acid copolymershaving pendent polysaccharide moieties.

BACKGROUND OF THE INVENTION

The primary objective of a cleaning composition is to remove soil froman article. In the case where the cleaning composition is a laundrydetergent and the article to be cleaned is not highly stained,surfactants, builders and enzymes formulated into most detergents areadequate to completely remove soil from the article. When strongercleaning power is needed to remove soil from the article other productssuch as bleach or laundry boosters are used in addition to thedetergent. In addition, washing with hotter water, using longer washcycles, pre-soaking the soiled article in an aqueous solution containingdetergent, or using a spot pretreater are helpful for removing soil.

However, where the article is heavily soiled, or where the soil haspenetrated into the article, surfactants, builders, enzymes, bleach, orlaundry boosters are not always completely effective in removing soilfrom an article. Spot pretreaters are useful, but they need to beapplied to the stained area prior to washing requiring an inconvenientadditional step in the washing process. Additionally, certain soils areparticularly difficult to remove from certain types of articles. Forexample, oil based soils are particularly difficult to remove fromsynthetic fabrics, and ground in clay or particulate stains areparticularly difficult to remove from cotton fabrics. In addition,removing soil can be made more difficult when soil which is suspended inthe washing process redeposits onto the article.

Soils commonly found on stained articles include oil and oilyparticulate stains such as frying oils or grease, sauces like tomato orspaghetti sauce, tea or coffee stains; non-saponifiable oil stains suchas used motor oil or petroleum oils; grass stains; enzyme sensitivestains such as fats or proteins; and mineral stains such as clays.

Several solutions have been proposed for improving the cleaning of anarticle. One proposed solution for cleaning of an article is to add a"soil removal agent" to a cleaning composition to increase soil removalfrom the article during cleaning. Another proposed solution involvesprotecting an article with a "soil resistant agent" so that soil is notdeposited as easily on the article in comparison to another article notprotected by the soil resistant agent. The soil resistant agent may alsoact to protect the article by making soil on an article easier to removein comparison to another article which was not protected by the soilresistance agent before being soiled. Another proposed solution involvesadding an agent which inhibits soil which has been removed from anarticle during cleaning from depositing onto the same or differentarticle.

U.S. Pat. No. 3,485,762 describes using styrene-maleic anhydridecopolymers derivatized with polyethylene glycols in detergentcompositions. While the detergent compositions are effective forremoving soil from hydrophobic articles such as polyester, suchcopolymers are not as effective on hydrophilic articles such as cotton.

U.S. Pat. No. 4,444,561 describes using copolymers prepared from 50 to90 weight percent of a vinyl ester of C₁ -C₄ aliphatic carboxylic acids,from 5 to 35 weight percent of a N-vinyl lactam, and from 1 to 20 weightpercent of a monomer containing basic nitrogen capable of forming a saltor quaternized product, in detergent compositions to inhibit soilredeposition. The disadvantage of using such copolymers, however, isthat they are capable of forming cations which may complex with anionicsurfactants under certain wash conditions and cause a decrease incleaning performance. In addition, the cationic copolymers may alsoundesirably promote fabric graying over multiple washing cycles.

U.S. Pat. No. 5,008,032 describes using copolymers prepared from C₄ -C₂₈olefins and α,β-ethylenically unsaturated dicarboxylic anhydrides indetergent formulations. The disadvantage of using such copolymers,however, is that the copolymers are not water-soluble unless hydrolyzedwith NaOH.

U.S. Pat. No. 5,580,941 describes the use of a water-soluble, acid-groupcontaining graft copolymer as a biodegradable builder in detergentformulations. The graft copolymer is obtained by copolymerizing amonomer mixture in the presence of a sugar. The monomer mixture containsa monoethylenically unsaturated C₃ to C₁₀ monocarboxylic acid, or saltthereof with a monovalent cation, and a monoethylenically unsaturatedmonomer comprising a monosulfonic acid group, monoethylenicallyunsaturated sulfuric acid ester, vinylphosphonic acid or salt thereofwith a monovalent cation. The disadvantage of using such copolymers,however, is that they do not have any soil release properties.

European Patent Application 753 570 A2 describes a soil removal and soilresistant detergent composition containing a vinyl amide polymer whichis prepared from 5 to 100 weight percent of a vinyl amide monomer andfrom 0 to 95 weight percent of a vinyl ester monomer. While thedetergent compositions are effective for removing soil from hydrophobicarticles such as polyester, such compositions are not as effective forcleaning hydrophilic substrates such as cotton.

U.S. patent application Ser. No. 09/025,002, filed Feb. 17, 1998,describes polymers having pendent polysaccharide moieties. The polymerbackbone is prepared from ethylenically unsaturated monomers by anaddition polymerization reaction.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the invention to provide a polymer whichimproves the cleaning properties of cleaning compositions by removingsoil.

It is another object of the invention to provide a polymer whichimproves the cleaning properties of cleaning compositions by inhibitingthe redeposition of soil from the cleaning process onto an article.

It is also an object of the invention to provide a polymer which impartssoil resistance to an article.

It is a further object of the invention to provide a polymer which iscompatible with other components used in a cleaning composition andwhich improves the cleaning properties of cleaning compositions byremoving soil from hydrophilic and hydrophobic articles.

With regard to the foregoing and other objects, the present inventionprovides a water-soluble or water-dispersible amino acid copolymerhaving pendent polysaccharide moieties having the structure ##STR1##wherein M⁺ is a cation selected from the group consisting of H+,ammonium, alkali metals, alkaline earth metals, Zn²⁺, Cu²⁺, quaternaryorganic amines, amino acids, and protonated amino saccharides; units[a], [b], [c], [d], [e] and [f] are present in random order; the molepercent of (a+b) is from 5 to 100; the mole percent of (c+d) is from 0to 95; the mole percent of (e) is from 0 to 95; the mole percent of (f)is from 0 to 95; R₁ and R₂ are independently selected from the groupconsisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, and asaccharide moiety having the structure (I) ##STR2## wherein R₅ ishydrogen or is represented by structure I(a) ##STR3## and R₆ is hydrogenor is represented by structure I(a) or structure I(b) ##STR4## providedthat at least one of R₁ or R₂ is a saccharide moiety; R₃ and R₄ areindependently selected from the group consisting of hydrogen, an alkylgroup having 1 to 12 carbon atoms, and a residue of an amino acid otherthan aspartic acid and glutamic acid; and (m+n) is greater than or equalto 0.

According to another aspect the invention provides a cleaningcomposition comprising a water-soluble or water-dispersible amino acidcopolymer having pendent polysaccharide moieties having the structure##STR5## wherein M⁺ is a cation selected from the group consisting ofH+, ammonium, alkali metals, alkaline earth metals, Zn²⁺, Cu²⁺,quaternary organic amines, amino acids, and protonated aminosaccharides; units [a], [b], [c], [d], [e] and [f] are present in randomorder; the mole percent of (a+b) is from 5 to 100; the mole percent of(c+d) is from 0 to 95; the mole percent of (e) is from 0 to 95; the molepercent of (f) is from 0 to 95; R₁ and R₂ are independently selectedfrom the group consisting of hydrogen, an alkyl group having 1 to 4carbon atoms, and a saccharide moiety; provided that at least one of R₁or R₂ is a saccharide moiety; R₃ and R₄ are independently selected fromthe group consisting of hydrogen, an alkyl group having 1 to 12 carbonatoms, and a residue of an amino acid other than aspartic acid andglutamic acid; and (m+n) is greater than or equal to 0.

According to another aspect the invention provides a method forpreparing the water-soluble or water-dispersible amino acid copolymerhaving pendent polysaccharide moieties, said method comprises: (I)dissolving at least one amino acid polymer having 5 to 100 mole percentof (f) units in a polar aprotic solvent to form a solution; (II) addingat least one amine containing polysaccharide to the solution formed inStep (I) to form a mixture, wherein the amine containing polysaccharidehas the structure ##STR6## and (III) heating the mixture formed in Step(II) at a temperature of from about 30° C. to about 120° C. for asufficient time to react the amino acid polymer with the aminecontaining polysaccharide. Preferably, the polar aprotic solvent isremoved from the amino acid copolymer having pendent polysaccharidemoieties by evaporation or precipitation.

According to another aspect the invention provides a method forpreparing the water-soluble or water-dispersible amino acid copolymerhaving pendent polysaccharide moieties, said method comprises: (I)forming a mixture comprising water, at least one amine containingpolysaccharide and at least one amino acid polymer having 5 to 100 molepercent of (f) units; and (II) heating the mixture at a pH greater than9 in the presence of a sufficient amount of base in order to maintainthe pH above 9 and at a temperature of from about 30° C. to about 100°C. for a sufficient time to react the amino acid polymer with the aminecontaining polysaccharide. Preferably the water is removed from theamino acid copolymer having pendent polysaccharide moieties byevaporation, freeze drying, or spray drying.

According to another aspect the invention provides a method forpreparing the water-soluble or water-dispersible amino acid copolymerhaving pendent polysaccharide moieties, said method comprises: (I)forming a mixture comprising water, at least one amine containingpolysaccharide and at least one amino acid polymer having 5 to 100 molepercent of (f) units; and (II) heating the mixture at a pH of less than12 and at a temperature of from about 30° C. to about 100° C. for asufficient time to react the amino acid polymer with the aminecontaining polysaccharide.

According to another aspect the invention provides a method of cleaningwhich involves preparing a cleaning composition comprising the aminoacid copolymer having pendent polysaccharide moieties, contacting thecleaning solution with one or more articles, wherein at least one of thearticles contains soil, and removing at least a portion of the soil fromthe article containing soil.

According to a further aspect the invention provides a method ofimparting soil resistance to an article which involves preparing acleaning composition comprising the amino acid copolymer having pendentpolysaccharide moieties, and contacting the cleaning composition withthe article to provide soil resistance to the article.

The amino acid copolymer having pendent polysaccharide moieties whenused in a cleaning process, removes soil from articles, inhibit soildeposition on articles, and provide soil resistance to articles.Examples of cleaning compositions containing the amino acid copolymershaving pendent polysaccharide moieties are laundry detergents,prespotters, dishwashing detergents, and hard surface cleaners. Theamino acid copolymers having pendent polysaccharide moieties aresufficiently hydrophobic to absorb to an article such as cloth in awashing process yet retain enough hydrophilic character to decrease thehydrophobic nature of an article such as polyester.

DESCRIPTION OF THE INVENTION

The water-soluble or water-dispersible amino acid copolymer havingpendent polysaccharide moieties has the structure ##STR7##

As used herein, "pendent" means that the amine containing polysaccharidemoieties are attached to the amino acid copolymer backbone. Pendentshould not be read in the strict sense which would exclude theattachment of such groups at the terminal end of a polymer chain.

In the above structure for the amino acid copolymer having pendentpolysaccharide moieties, M⁺ is a cation selected from the groupconsisting of H⁺, ammonium, alkali metals, alkaline earth metals, Zn²⁺,Cu²⁺, quaternary organic amines, amino acids, and protonated aminosaccharides.

The units [a], [b], [c], [d], [e] and [f] are present in random order.The mole percent of (a+b) is from 5 to 100, preferably from 10 to 50,more preferably from 15 to 30. The mole percent of (c+d) is from 0 to95, preferably from 50 to 90, more preferably from 70 to 85. The molepercent of (e) is from 0 to 90. The mole percent of (f) is from 0 to 90.The (f) units are derived from glutamic acid and/or aspartic acid.

R₁ and R₂ are independently selected from the group consisting ofhydrogen, an alkyl group having 1 to 4 carbon atoms, and a saccharidemoiety having the structure (I) ##STR8## wherein R₅ is hydrogen orrepresented by structure I(a) ##STR9## and R₆ is hydrogen or isrepresented by structure I(a) or structure I(b) ##STR10## provided thatat least one of R₁ or R₂ is a saccharide moiety.

The saccharide moiety may be a amine containing polysaccharide or amonosaccharide moiety. The amino acid polymer having pendentpolysaccharide moieties may be prepared with a combination ofpolysaccharide moieties and monosaccharide moieties. The saccharidemoiety is derived from a saccharide which is selected from the groupconsisting of starches, hydrolyzed starches, glucose, lactose, maltose,maltodextrins, corn syrup solids, cellulose, hydrolyzed celluose,dextran, hydrolyzed dextran, guar gum, hydrolyzed guar gum, locust beangum, hydrolyzed locust bean gum, and combinations thereof. Suitablestarches include, for example, corn, potato, tapioca, and rice.

The sum of (m+n) is greater than or equal to 0. Preferably, the sum of(m+n) is from 0 to 1000. More preferably, the sum of (m+n) is from 2 to20.

R₃ and R₄ are independently selected from the group consisting ofhydrogen, an alkyl group having 1 to 12 carbon atoms, and a residue ofan amino acid other than aspartic acid and glutamic acid. Preferably R₃and R₄ are independently selected from the group consisting of an aminoalkyl, (aminoiminomethyl)amino alkyl, (1H-imidazol-4-yl) alkyl, aminooxo alkyl, hydrogen, an alkyl group having 1 to 12 carbon atoms, phenylalkyl, (hydroxyphenyl)alkyl, indole alkyl, hydroxy alkyl, mercaptoalkyl, and (methylthio) alkyl. More preferably, R₃ and R₄ areindependently selected from the group consisting of 4-aminobutyl,3-[(aminoiminomethyl)amino]propyl, (2-amino-2-oxoethyl,3-amino-3-oxopropyl, hydrogen, methyl, 1-(methyl)ethyl,2-(methyl)propyl, 1-(methyl)propyl, phenylmethyl(4-hydroxyphenyl)methyl, indole methyl, hydroxymethyl, mercaptomethyl,1-(hydroxy)ethyl, and 2-(methylthio)ethyl.

The amino acid copolymer having pendent polysaccharide moieties hasrepeating units selected from the group consisting of aspartic acid,glutamic acid and combinations thereof and, optionally, additionalrepeating units selected from the groups consisting natural andsynthetic amino acids. Examples of natural amino acids include lysine,arginine, histidine, asparagine, glutamine, proline, glycine, alanine,valine, leucine, isoleuscine, phenylalanine, tyrosine, tryptophan,serine, cysteine, threonine, methionine, and cystine. Examples ofsynthetic amino acids include amino benzoic acid, 6-amino hexanoic acid,and 11-amino undecanoic acid.

In one embodiment of the invention, R₁ is a saccharide moiety having thestructure (I); R₅ and R₆ are hydrogen; and R₂ is hydrogen or an alkylgroup having 1 to 4 carbon atoms.

In one embodiment of the invention, R₁ is a saccharide moiety having thestructure (I); R₅ is represented by structure I(a); R₆ is hydrogen; R₂is hydrogen or an alkyl group having 1 to 4 carbon atoms; and m=1.

In one embodiment of the invention, R₁ is a saccharide moiety having thestructure (I); R₅ is hydrogen or is represented by structure I(a); R₆ ishydrogen or is represented by structure I(a) or structure I(b); R₂ ishydrogen or an alkyl group having 1 to 4 carbon atoms; and (m+n) is2-20.

In one embodiment of the invention, the amine containing polysaccharideis prepared by reductive amination of a saccharide containing a reducingend group with at least one compound selected from the group consistingof ammonia, a primary amine, hydrazine, and hydroxyl amine. Preferablythe reductive amination reaction is conducted in water without acosolvent and involves mixing a saccharide with an amine in water, andthen contacting the mixture with pressurized hydrogen in the presence ofa Group VIIIB metal catalyst and under conditions effective to producean amino saccharide. Methods for preparing the amine containingpolysaccharide are disclosed in U.S. Pat. No. 5,654,198 which isincorporated herein by reference.

The water-soluble or water-dispersible amino acid polymer with pendentsaccharide moieties is prepared by either condensing an aspartic acid orglutamic acid copolymer with an amine containing saccharide to form amodified amino acid polymer or by the ring opening reaction of an aminecontaining saccharide with a succinimide copolymer or glutimidecopolymer. The time of reaction according to the present invention ispreferably from about 10 minutes to 48 hours, more preferably from about1 hour to about 8 hours.

In one embodiment of the invention, the water-soluble orwater-dispersible amino acid copolymer having pendent polysaccharidemoieties is prepared by a method comprising: (I) dissolving at least oneamino acid polymer having 5 to 100 mole percent of (f) units in a polaraprotic solvent to form a solution; (II) adding at least one aminecontaining polysaccharide to the solution formed in Step (I) to form amixture, wherein the amine containing polysaccharide has the structure##STR11## and (III) heating the mixture formed in Step (II) at atemperature of from about 30° C. to about 120° C. for a sufficient timeto react the amino acid polymer with the amine containingpolysaccharide. Preferably, the polar aprotic solvent is removed fromthe amino acid copolymer having pendent polysaccharide moieties byevaporation or precipitation.

While not wishing to be bound by any particular theory, the inventorsbelieve that the amine containing saccharide reacts by means of acondensation reaction with the (f) units on the amino acid polymer toform (a) and (b) units.

In one embodiment of the invention, the water-soluble orwater-dispersible amino acid copolymer having pendent polysaccharidemoieties is prepared by a method comprising: (I) forming a mixturecomprising water, at least one amine containing polysaccharide and atleast one amino acid polymer having 5 to 100 mole percent of (f) units;and (II) heating the mixture at a pH greater than 9 in the presence of asufficient amount of base in order to maintain the pH above 9 and at atemperature of from about 30° C. to about 100° C. for a sufficient timeto react the amino acid polymer with the amine containingpolysaccharide. Preferably the water is removed from the amino acidcopolymer having pendent polysaccharide moieties by evaporation, freezedrying, or spray drying.

A preferred base is sodium hydroxide. While not wishing to be bound byany particular theory, the inventors believe that the amine containingsaccharide reacts by means of a condensation reaction with the (f) unitson the amino acid polymer to form (a) and (b) units, and water reactswith the (f) units to form (c) and (d) units. It is noted that theproduct contains water, an amino acid polymer having pendentpolysaccharide moieties and possible some unreacted amino saccharideunits or unreacted amino acid polymer. M+ is expected to be theconjugate acid of the added base. For example, M+ is Na+ if the addedbase is NaOH.

In one embodiment of the invention, the water-soluble orwater-dispersible amino acid copolymer having pendent polysaccharidemoieties is prepared by a method comprising: (I) forming a mixturecomprising water, at least one amine containing polysaccharide and atleast one amino acid polymer having 5 to 100 mole percent of (f) units;and (II) heating the mixture at a pH of less than 12 and at atemperature of from about 30° C. to about 100° C. for a sufficient timeto react the amino acid polymer with the amine containingpolysaccharide. It is noted that the pH of the reaction in thisembodiment is not adjusted and as a result is generally within the rangeof from about 7 to about 11. While not wishing to be bound by anyparticular theory, the inventors believe that M+ in this embodiment is aprotonated amine containing polysaccharide. The water is removed bymethods known in the art such as by evaporation.

In a preferred embodiment of the invention, the amino acid copolymerhaving pendent polysaccharide moieties is prepared by reacting eitherN-methyl glucamine or 1-amino-1-deoxy-D-sorbitol with polysuccinimide.

In a preferred embodiment of the invention, the amino acid copolymerhaving pendent polysaccharide moieties is prepared by reacting eitherN-methyl lactamine, N-methyl maltamine, lactamine or maltamine withpolysuccinimide.

In a preferred embodiment of the invention, the amino acid copolymerhaving pendent polysaccharide moieties is prepared by reacting eitherN-methyl amino corn syrup solids, amino corn syrup solids, N-methylamino maltodextrin or amino maltodextrin with polysuccinimide.

The amino acid copolymer product having pendent polysaccharide moietiesin solution generally has a pH of from 3 to 9, preferably from about 8to 9. It is noted that a pH outside of this range for an extended periodof time after the polymer product is prepared subjects the polymer todegradation.

The amino acid copolymer having pendent polysaccharide moieties may beused in any cleaning composition. As used herein, "clean" means toremove soil from an article, inhibit soil deposition in a cleaning orwashing process, or provide soil resistance to an article orcombinations thereof. Articles which may be cleaned using the amino acidcopolymers are articles which come into contact with soil and which arecapable of being cleaned in a cleaning process. Examples of sucharticles include fabrics, such as clothing, linens, carpets, orupholstery; hard surfaces such as countertops, windows, floors, dishes,glasses or tiles; or automobiles.

The cleaning composition may be a solid or liquid composition. If thecleaning composition is solid, the cleaning composition may be in any ofthe usual physical forms, such as for example, powders, beads, flakes,bars, tablets, noodles, pastes, and slurries. If the cleaningcomposition is liquid, the cleaning composition preferably disperses orsolubilizes the amino acid copolymer having pendent polysaccharidemoieties so that it is easily contacted with the article. The cleaningcomposition may be aqueous or nonaqueous. For example, the amino acidcopolymer having pendent polysaccharide moieties may be dissolved ordispersed in water, in one or more solvents or inert diluents.Preferably the cleaning composition is aqueous. The cleaning compositionpreferably contains the amino acid copolymer having pendentpolysaccharide moieties in an amount of from about 1 to about 60 weightpercent, more preferably from about 2 to about 20 weight percent, basedon the total weight of the cleaning composition.

The cleaning compositions may contain any additional components whichare used in cleaning compositions. Such additional components are wellknown to those skilled in the art and include one or more surfactants,builders, ion exchangers, alkalies, anticorrosion materials,antiredeposition materials, optical brighteners, fragrances, dyes,chelating agents, enzymes, whiteners, brighteners, antistatic agents,sudsing control agents, solvents, hydrotropes, bleaching agents,perfumes, bleach precursors, water, buffering agents, soil removalagents, soil release agents, softening agents, opacifiers, inertdiluents, buffering agents, corrosion inhibitors, graying inhibitors,anti-redeposition agents, stabilizers, opacifiers, fillers, builders,phosphate co-builder, and phosphate-replacer builder. Combinations ofsuch additional components may also be used.

Preferably cleaning compositions prepared using the amino acidcopolymers having pendent polysaccharide moieties contain at least onesurfactant. Suitable surfactants include nonionic, anionic, cationic,and amphoteric surfactants. The surfactants usable in the cleaningcomposition may also be soaps.

Anionic surfactants include, for example, from C₈ to C₁₂alkylbenzenesulfonates, from C₁₂ to C₁₆ alkanesulfonates, from C₁₂ toC₁₆ alkysulfates, from C₁₂ to C₁₆ alkylsulfosuccinates or from C₁₂ toC₁₆ sulfated ethoxylated alkanols.

Nonionic surfactants include, for example, from C₆ to C₁₂ alkylphenolethoxylates, from C₁₂ to C₂₀ alkanol alkoxylates, and block copolymersof ethylene oxide and propylene oxide. Optionally, the end groups ofpolyalkylene oxides can be blocked, whereby the free OH groups of thepolyalkylene oxides can be etherified, esterified, acetalized and/oraminated. Another modification consists of reacting the free OH groupsof the polyalkylene oxides with isocyanates. The nonionic surfactantsalso include C₄ to C₁₈ alkyl glucosides as well as the alkoxylatedproducts obtainable therefrom by alkoxylation, particularly thoseobtainable by reaction of alkyl glucosides with ethylene oxide.

Cationic surfactants contain hydrophilic functional groups where thecharge of the functional groups are positive when dissolved or dispersedin an aqueous solution. Typical cationic surfactants include, forexample, amine compounds, oxygen containing amines, and quaternary aminesalts.

Amphoteric surfactants contain both acidic and basic hydrophilic groups.Amphoteric surfactants are preferably derivatives of secondary andtertiary amines, derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. The cationic atom in thequaternary compound can be part of a heterocyclic ring. The amphotericsurfactant preferably contains at least one aliphatic group, containingabout 3 to about 18 carbon atoms. At least one aliphatic grouppreferably contains an anionic water-solubilizing group such as acarboxy, sulfonate, or phosphono.

Generally, anionic surfactants, such as linear alkyl sulfonates (LAS)are preferred for use in solid cleaning compositions containing theamino acid copolymers having pendent polysaccharide moieties. Nonionicand anionic surfactant mixtures such as alcohol ethoxylates and LAS arepreferred in liquid cleaning compositions containing the amino acidcopolymers having pendent polysaccharide moieties. The surfactants areoptionally present in an amount of from about 0 to about 50 weightpercent, preferably from about 2 to about 45 weight percent, and morepreferably from about 5 to about 40 weight percent of the cleaningcomposition.

Examples of builders which may be present in the cleaning compositioninclude, for example, phosphates, such as pyrophophates, polyphosphates,or sodium tripolyphosphate. Further examples are zeolites, sodiumcarbonate, poly(carboxylic acids), nitrilotriacetic acid, citric acid,tartaric acid, the salts of the aforesaid acids and the monomeric,oligomeric, or polymeric phosphonates. Combinations of builders may alsobe used. The builders are optionally present in an amount of from 0 toabout 85 weight percent, preferably from about 5 to about 50 weightpercent based on the total weight of the cleaning composition.

Liquid cleaning compositions containing the amino acid copolymers havingpendent polysaccharide moieties can contain up to 80 weight percentwater or solvents or combinations thereof. Typical solvents which may beused include oxygen containing solvents such as alcohols, ester, glycol,and glycol ethers. Alcohols that may be used in the cleaningcompositions include, for example, methanol, ethanol, isopropanol, andtertiary butanol. Esters which may be used include, for example, amylacetate, butyl acetate, ethyl acetate, and esters of glycols. Glycolsand glycol ethers that are useful as solvents include, for example,ethylene glycol, propylene glycol, and oligomers of ethylene orpropylene glycol.

Solid cleaning compositions containing the amino acid copolymers havingpendent polysaccharide moieties preferably contain up to 60 weightpercent of one or more solid inert diluents such as sodium sulfate,sodium chloride, sodium borate, or selected polymers such aspolyethylene glycol or propylene glycol.

The cleaning composition may contain 0 to about 50 weight percent of oneor more buffering agents. Buffering agents include, for example, one ormore alkali metal salts such as silicates, carbonates, or sulfates.Buffering agents also include, for example, organic alkalis such astriethanolamine, monoethanolamine, and triisopropanolamine.

Fabric softening agents typically include quaternary ammonium salts suchas ditallowdimethyl-ammonium chloride.

Other additives which optionally may be included in the cleaningcompositions especially for detergent compositions are bleaching agents,used in an amount of up to about 30 weight percent, corrosion inhibitorssuch as silicates used in an amount of up to about 25 weight percent,dye deposition inhibiting agents used in an amount up to about 20 weightpercent, and graying inhibitors used in an amount of up to about 5weight percent.

Suitable bleaching agents are, for example, perborates, percarbonates,or chlorine-generating substances such as chloroisocyanurates. Suitablesilicates used as corrosion inhibitors are, for example, sodiumsilicate, sodium disilicate, and sodium metasilicate. Suitable dyedeposition inhibiting agents are, for example, polyvinyl pyrrolidone.Examples of graying inhibitors are, for example, carboxymethylcellulose,methylcellulose, hydroxypropylmethylcellulose, and graft copolymers ofvinyl acetate and polyalkylene oxides having a molecular weight of 1,000to 15,000.

The cleaning composition containing the amino acid copolymers havingpendant polysaccharide moieties is contacted with one or more articles,where at least one article contains soil. Contacting can be carried out,for example, by immersing the articles in the cleaning composition andagitating the articles in the cleaning composition containing thepolymer. Contacting can also be accomplished by wiping, spraying, orpadding the cleaning composition on the articles.

In a preferred embodiment of the invention, the amino acid copolymerhaving pendant polysaccharide moieties is incorporated in a detergentformulation. In a detergent formulation, the amino acid copolymershaving pendent polysaccharide moieties are preferably present in anamount of from about 0.1 to about 25 weight percent, more preferablyfrom about 0.5 to about 10 weight percent, and most preferably fromabout 1 to about 5 weight percent, based on the total weight of thedetergent formulation. When the detergent formulation is a laundrydetergent, the amino acid copolymers having pendant polysaccharidemoieties function to reduce the amount of oily soil that can adhere tothe cloth. Subsequent washing of the cloth will remove more soil as aresult of the reduced interactions between the soil and the cloth.

In another preferred embodiment of the invention, the amino acidcopolymers having pendent polysaccharide moieties are incorporated intoa prespotter formulation for direct application to a soiled fabric orcarpet. The amino acid copolymers aid in removal of soil from fabriceven if the fabric is washed in a laundry detergent which does notcontain the polymers. When used in a prespotter formulation, the aminoacid copolymers having pendent polysaccharide moieties are preferablypresent in an amount of from about 0.5 to about 75 weight percent, morepreferably from about 1 to about 15 weight percent, and most preferablyfrom about 2 to about 10 weight percent, based on the total weight ofthe prespotter formulation.

In another preferred embodiment of the invention, the amino acidcopolymers having pendent polysaccharide moieties are incorporated intoa fabric softening composition. The amino acid copolymers aid in releaseof soil during fabric softening.

The following nonlimiting examples illustrate further aspects of theinvention.

EXAMPLE 1 Synthesis of Amino Acid Polymer A Having PendentPolysaccharide Moieties ##STR12## wherein=1.

Poly(succinimide) with a weight average molecular weight of 30,000 wasdried in an oven at 100° C. for 1 hr. and then cooled in a dessicator. Afour-neck round bottom flask was equipped with a mechanical stirrer,thermometer, stopper and nitrogen inlet topped reflux condenser. To theround bottom flask, was charged 50 g (0.52 mole imide functionality) ofthe cool, dried poly(succinimide) and 390 g dimethyl sulfoxide whilemaintaining a positive pressure of nitrogen in the flask. The resultingmixture was warmed under a positive pressure of nitrogen to 60° C. andstirred until the poly(succinimide) had completely dissolved. To thehomogenous mixture was then added 80.5 g (0.41 mole) N-methyl glucamine.Stirring under a positive pressure of nitrogen at 60° C. was continued.The progress of the reaction was followed by titrating aliquots of thereaction mixture for free amine with 0.1 N HCl. After 38 hrs. at 60° C.,the reaction was determined to be complete.

The reaction product was precipitated by pouring the cooled reactionmixture into four volumes of methanol and then collected by vacuumfiltration. The reaction product was washed with methanol and then driedin a forced air oven at 50° C. The yield of light brown powder was 91.0g. Analysis by carbon-13 NMR indicated that the product contained 30mole percent succinimide residues (f sub-units, x=1) and 70 mole percentamide residues (a+b sub-units, x=1).

EXAMPLE 2 Synthesis of Amino Acid Polymer B Having PendentPolysaccharide Moieties ##STR13## wherein x=1.

Poly(succinimide) with a weight average molecular weight of 30,000 wasdried in an oven at 100° C. for 1 hr. and then cooled in a dessicator. Afour-neck round bottom flask was equipped with a mechanical stirrer,thermometer, pH electrode, and reflux condenser. To the round bottomflask, was charged 30 g (0.31 mole imide functionality) of the cool,dried poly(succinimide), 250 g deionized water, and 56.0 g (0.31 mole)1-amino-1-deoxy-D-sorbitol. The resulting mixture was warmed to 60° C.,and 3.89 N NaOH was added at a rate such as to keep the reaction pH at11.0 using an automatic pH controller. The reaction temperature wasallowed to cool gradually over 4.5 hr. while the pH was maintained at11.0. After 4.5 hr. of heating, the temperature was 40° C., 72.5 ml(0.282 moles) of 3.89 N NaOH had been added, and the solution wasessentially clear. After it had cooled to room temperature (˜20° C.),the pH of the solution was lowered to 10.6 by the addition ofconcentrated hydrochloric acid. The solution was then filtered in orderremove a small amount of insoluble material.

About 15 g of the reaction mixture was then treated with AMBERLITE IR120 (plus) strongly acidic ion exchange resin in order to remove unbound1-amino-1-deoxy-D-sorbitol and then freeze dried. The solid obtained inthis manner was then analyzed by proton NMR. The reaction product wasfound to be poly(aspartic acid) modified with 43 mole percent covalentlybound 1-amino-1-deoxy-D-sorbitol; 43 mole percent amide residues (a+bsub-units, x=1) and 57 mole percent aspartic acid, sodium salt residues(c+d units with M+=Na+, x=1).

EXAMPLE 3 Synthesis of Amino Acid Polymer C Having PendentPolysaccharide Moieties ##STR14## wherein x=1.

Poly(succinimide) with a weight average molecular weight of 30,000 wasdried in an oven at 100° C. for 1 hr. and then cooled in a dessicator. Afour-neck round bottom flask was equipped with a mechanical stirrer,thermometer, pH electrode, and reflux condenser. To the round bottomflask, was charged 30 g (0.31 mole imide functionality) of the cool,dried poly(succinimide) and 270 g deionized water, and 60.3 g (0.31mole) N-methyl-D-glucamine. The resulting mixture was warmed to 38° C.,and 3.89 N NaOH was added at a rate such as to keep the reaction pH at11.0 using an automatic pH controller. The reaction was heated to 48 to52° and held for 4.5 hr. and then allowed to cool to room temperature.After 4.5 hr. of heating, the temperature was 48° C., 78.6 ml (0.305moles) of 3.89 N NaOH had been added, and the solution was essentiallyclear. After it had cooled to room temperature (˜20° C.), the pH of thesolution was lowered to 10.71 by the addition of concentratedhydrochloric acid. The solution was then filtered in order remove asmall amount of insoluble material.

About 15 g of the reaction mixture was then treated with AMBERLITE IR120 (plus) strongly acidic ion exchange resin in order to remove unbound1-amino-1-deoxy-D-sorbitol and then freeze dried. The solid obtained inthis manner was then analyzed by proton NMR. The product was found to bepoly(aspartic acid) modified with 13 mole percent covalently boundN-methyl glucamine; 13 mole percent amide residues (a+b sub-units, x=1)and 87 mole percent aspartic acid, sodium salt residues (c+d units withM+=Na+, x=1).

EXAMPLE 4 Synthesis of Amino Acid Polymer D Having PendentPolysaccharide Moieties ##STR15## wherein x=1.

A four-neck 500 ml round bottom flask was equipped with a mechanicalstirrer, thermometer, stopper, and nitrogen inlet-topped refluxcondenser. To the round bottom flask, was charged 30 g (0.31 mole imidefunctionality) of poly(succinimide) with a weight average molecularweight of 30,000 and 270 g deionized water, and 60.3 g (0.31 mole)N-methyl-D-glucamine. The resulting mixture was gradually warmed to 78°C. and maintained at this temperature for 32 hr. After 24 hr. heating,the reaction mixture was essentially clear. After 32 hr., analysis of analiquot of the reaction mixture indicated that there only about 7% ofthe N-methyl glucamine remained free (neither ionically nor covalentlybound to the poly(aspartic acid) derivative). After the reaction hadcooled to room temperature (˜20° C.), it was filtered and then freezedried.

The yield of solid product was 70 g. Analysis by liquid chromatographyindicated that the poly(aspartic acid) polymer was modified with about11 mole percent covalently bound N-methyl glucamine; 11% amide residue(a+b sub-units, x=1) and 89% aspartic acid, N-methyl glucammonium saltresidues (c+d units with M+=N-methyl glucammonium+, x=1).

EXAMPLE 5 Synthesis of Amino Acid Polymer E Having PendentPolysaccharide Moieties ##STR16## wherein x=1.

A four-neck 500 ml round bottom flask was equipped with a mechanicalstirrer, thermometer, stopper, and nitrogen inlet-topped refluxcondenser. To the round bottom flask, was charged 30 g (0.31 mole imidefunctionality) of poly(succinimide) with a weight average molecularweight of 30,000 and 250 g deionized water, and 56.0 g (0.31 mole)1-amino-1-deoxy-D-sorbitol. The resulting mixture was gradually warmedto 80° C. and maintained at this temperature for a total of 14 hr. After5 hr. of heating, the reaction mixture was essentially clear. After 13hr., analysis of an aliquot of the reaction mixture indicated that onlyabout 8% of the 1-amino-1-deoxy-D-sorbitol remained free (neitherionically nor covalently bound to the poly(aspartic acid) derivative).After the reaction had cooled to room temperature (˜20° C.), it wasfiltered and then freeze dried.

The yield of solid product was 64.0 g. Analysis by proton NMR and liquidchromatography indicated that the poly(aspartic acid) polymer wasmodified with about 24 mole percent covalently bound1-amino-1-deoxy-D-sorbitol; 24% amide residue (a+b sub-units, x=1) and76% aspartic acid, 1-ammonium-1-deoxy-D-sorbitol salt residues (c+dunits with M+=1-ammonium-1-deoxy-D-sorbitol+, x=1).

EXAMPLE 6 Synthesis of Amino Acid Polymer F Having PendentPolysaccharide Moieties ##STR17## wherein x=1

A four neck round bottom flask was equipped with a mechanical stirrer,thermometer, stopper and nitrogen inlet topped reflux condenser. To theround bottom flask, was charged 10 g (0.10 mole imide functionality) ofpoly(succinimide) with a weight average molecular weight of 30,000 and339 g dimethyl sulfoxide while maintaining a positive pressure ofnitrogen in the flask. The resulting mixture was warmed under a positivepressure of nitrogen to 30° C. and stirred until the poly(succinimide)had completely dissolved. To the homogenous mixture was then added 103 g(0.05 mole) N-methylamino maltodextrin (number average molecular weightof about 2000). Stirring under a positive pressure of nitrogen at wascontinued and the temperature was gradually raised to 60° C. Theprogress of the reaction could be followed by titrating aliquots of thereaction mixture for free amine with 0.1 N HCl. After about 48 hr.reaction time, about half of the N-methylamino maltodextrin had reactedwith poly(succinimide). The product was precipitated by pouring thecooled reaction mixture into 4 volumes of methanol and then collected byvacuum filtration. The product was washed with methanol and then driedin a forced air oven at 40° C. The yield of solid product was 81.7 g.The product was characterized by proton and carbon NMR and found tocontain amide residues (a+b sub-units, x=1), succinimide residues (fsub-units, x=1), and N-methylamino maltodextrin.

EXAMPLE 7 Synthesis of Amino Acid Polymer G Having PendentPolysaccharide Moieties ##STR18##

Poly(succinimide) with a weight average molecular weight of 30,000 isdried in an oven at 100° C. for 1 hr. and then cooled in a dessicator. Afour neck round bottom flask is equipped with a mechanical stirrer,thermometer, stopper and nitrogen inlet topped reflux condenser. To theround bottom flask, is charged 50 g (0.52 mole imide functionality) ofthe cool, dried poly(succinimide) and 390 g dimethyl sulfoxide whilemaintaining a positive pressure of nitrogen in the flask. The resultingmixture is warmed under a positive pressure of nitrogen to 60° C. andstirred until the poly(succinimide) completely dissolves. To thehomogenous mixture is then added 92.8 g (0.26 mole) N-methyl lactamine.Stirring under a positive pressure of nitrogen at 60° C. is continued.The progress of the reaction is followed by titrating aliquots of thereaction mixture for free amine with 0.1 N HCl. When the reaction iscomplete, the product is precipitated from the reaction mixture bypouring the cooled reaction mixture into 4 volumes of methanol and thencollected by vacuum filtration. The product is washed with methanol andthen dried in a forced air oven at 50° C.

EXAMPLE 8

The polymers prepared in Examples 1 and 5 were evaluated for soilrelease in a TERG-O-TOMETER test. Three cotton swatches were washed toremove the original textile finish. The initial L, a, and b values foreach of the swatches was measured using a Minolta colorimeter. Theswatches in each TERG-O-TOMETER were washed using 0.5 g/L of GREENCAREdetergent (commercially available from Sainsbury in England), 10 weightpercent, based on the weight of detergent, of Polymer A or Polymer E,except that no polymer was used to wash the control swatch, 110 ppmhardness water based on MgCl and CaCl, 93° F. and stirred at 80 rpm. A20 minute wash and a 3 minute rinse were used. Each of the swatches wasdried in a print drier or a standard clothes drier and then stained withspaghetti sauce (RAGU traditional). The stains were allowed to setovernight. The L, a and b values for each of the stained swatches wasmeasured.

The stained swatches were washed using 0.9 g/L of GREENCARE detergent,10 weight percent, based on the weight of detergent, of Polymer A orPolymer E, except that no polymer was used to wash the control swatch,110 ppm hardness water based on MgCl₂ and CaCl₂, 93° F. and stirred at80 rpm. A 20 minute wash and a 3 minute rinse were used. Each of theswatches was dried in a print drier or a standard clothes drier. The L,a and b values for each of the swatches was measured.

The ΔE for the stain on each swatch was calculated from the followingequation:

    ΔE=[(L.sub.1 -L.sub.2).sup.2 +(a.sub.1 -a.sub.2).sup.2 +(b.sub.1 -b.sub.2).sup.2 ].sup.0.5

The percent soil removal for each swatch was calculated from thefollowing equation: ##EQU1## wherein ΔEa-s is the difference in E afterthe stain is put on and after the swatch with the stain is washed andΔEb-s is the difference between after the stain is put on and no stainat all. The soil removal test results for each of the swatches issummarized in Table I.

                  TABLE I                                                         ______________________________________                                                                  Average %                                             Copolymer % Soil Removal Soil Removal                                       ______________________________________                                        Control       50.87       53.92                                                 (No polymer) 57.00                                                             53.91                                                                        Polymer E 62.91 59.19                                                          56.05                                                                         58.60                                                                        Polymer A 58.13 56.64                                                          54.92                                                                         56.88                                                                      ______________________________________                                    

The test results in Table I clearly show that Polymers A and E whichwere prepared in Examples 1 and 5, respectively, provided the cottonswatches with excellent soil release. In addition, Polymers A and Eprovided the cotton swatches with significantly greater soil releasethan the Control swatch which was stained and washed in detergent butwithout the polymer of the present invention.

While the invention has been described with particular reference tocertain embodiments thereof, it will be understood that changes andmodifications may be made by those of ordinary skill in the art withinthe scope and spirit of the following claims.

What is claimed is:
 1. A water-soluble or water-dispersible amino acid copolymer having pendent polysaccharide moieties having the structure ##STR19## wherein x is independently 1 or 2; M⁺ is a cation selected from the group consisting of H+, ammonium, alkali metals, alkaline earth metals, Zn²⁺, Cu²⁺, quaternary organic amines, amino acids, and protonated amino saccharides; units [a], [b], [c], [d], [e] and [f] are present in random order; the mole percent of (a+b) is from 5 to 100; the mole percent of (c+d) is from 0 to 95; the mole percent of (e) is from 0 to 95; the mole percent of (f) is from 0 to 95; R₁ and R₂ are independently selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, and a saccharide moiety having the structure (I) ##STR20## wherein R₅ is hydrogen or is represented by structure I(a) ##STR21## and R₆ is hydrogen or is represented by structure I(a) or structure I(b) ##STR22## provided that at least one of R₁ or R₂ is a saccharide moiety; R₃ and R₄ are independently selected from the group consisting of hydrogen, an alkyl group having 1 to 12 carbon atoms, and a residue of an amino acid other than aspartic acid and glutamic acid; and (m+n) is greater than or equal to
 0. 2. The amino acid copolymer according to claim 1 wherein R₃ and R₄ are independently selected from the group consisting of an amino alkyl, (aminoiminomethyl)amino alkyl, (1H-imidazol-4-yl)alkyl, amino oxo alkyl, hydrogen, an alkyl group having 1 to 12 carbon atoms, phenyl alkyl, (hydroxyphenyl)alkyl, indole alkyl, hydroxy alkyl, mercapto alkyl, and (methylthio)alkyl.
 3. The amino acid copolymer according to claim 2 wherein R₃ and R₄ are independently selected from the group consisting of 4-aminobutyl, 3-[(aminoiminomethyl)amino]propyl, (2-amino-2-oxoethyl, 3-amino-3-oxopropyl, hydrogen, methyl, 1-(methyl)ethyl, 2-(methyl)propyl, 1-(methyl)propyl, phenylmethyl(4-hydroxyphenyl)methyl, indole methyl, hydroxymethyl, mercaptomethyl, 1-(hydroxy)ethyl, and 2-(methylthio)ethyl.
 4. A method for preparing the water-soluble or water-dispersible amino acid copolymer having pendent polysaccharide moieties according to claim 1, wherein said method comprises:(I) dissolving at least one amino acid polymer having 5 to 100 mole percent of (f) units in a polar aprotic solvent to form a solution; (II) adding at least one amine containing polysaccharide to the solution formed in Step (I) to form a mixture, wherein the amine containing polysaccharide has the structure ##STR23## and (III) heating the mixture formed in Step (II) at a temperature of from about 30° C. to about 120° C. for a sufficient time to react the amino acid polymer with the amine containing polysaccharide.
 5. The method according to claim 4 wherein the polar aprotic solvent is removed from the amino acid copolymer having pendent polysaccharide moieties by evaporation or precipitation.
 6. A method for preparing the water-soluble or water-dispersible amino acid copolymer having pendent polysaccharide moieties according to claim 1, wherein said method comprises:(I) forming a mixture comprising water, at least one amine containing polysaccharide and at least one amino acid polymer having 5 to 100 mole percent of (f) units, wherein the amine containing polysaccharide has the structure ##STR24## and (II) heating the mixture at a pH greater than 9 in the presence of a sufficient amount of base in order to maintain the pH above 9 and at a temperature of from about 30° C. to about 100° C. for a sufficient time to react the amino acid polymer with the amine containing polysaccharide.
 7. The method according to claim 6 wherein the water is removed from the amino acid copolymer having pendent polysaccharide moieties by a method selected from the group consisting of evaporation, freeze drying, and spray drying.
 8. A method for preparing the water-soluble or water-dispersible amino acid copolymer having pendent polysaccharide moieties according to claim 1, wherein said method comprises:(I) forming a mixture comprising water, at least one amine containing polysaccharide and at least one amino acid polymer having 5 to 100 mole percent of (f) units, wherein the amine containing polysaccharide has the structure ##STR25## and (II) heating the mixture at a pH of less than 12 and at a temperature of from about 30° C. to about 100° C. for a sufficient time to react the amino acid polymer with the amine containing polysaccharide.
 9. The method according to claim 8, wherein the water is removed from the amino acid copolymer having pendent polysaccharide moieties by a method selected from the group consisting of evaporation, freeze drying, and spray drying.
 10. The amino acid copolymer according to claim 1 wherein the amino acid polymer has repeating units selected from the group consisting of aspartic acid, glutamic acid and combinations thereof.
 11. The amino acid copolymer according to claim 1 wherein the amino acid polymer has repeating units selected from the group consisting of aspartic acid, lysine, glutamic acid, arginine, histidine, asparagine, glutamine, proline, alanine, isoleucine, tyrosine, cysteine, methionine, tryptophan, cystine, and combinations thereof, provided that at least one repeating unit is aspartic acid or glutamic acid.
 12. The amino acid copolymer according to claim 1 wherein the saccharide moiety is derived from a saccharide which is selected from the group consisting of starches, hydrolyzed starches, glucose, lactose, maltose, maltodextrins, corn syrup solids, cellulose, hydrolyzed cellulose, dextran, hydrolyzed dextran, guar gum, hydrolyzed guar gum, locust bean gum, hydrolyzed locust bean gum, and combinations thereof.
 13. The amino acid copolymer according to claim 1 wherein R₁ is a saccharide moiety having the structure (I); R₅ and R₆ are hydrogen; and R₂ is hydrogen or an akyl group having 1 to 4 carbon atoms.
 14. The amino acid copolymer according to claim 13 which is prepared by reacting N-methyl glucamine or 1-amino-1-deoxy-D-sorbitol with polysuccinimide.
 15. The amino acid copolymer according to claim 1 wherein R₁ is a saccharide moiety having the structure (I); R₅ is represented by structure I(a); R₆ is hydrogen; R₂ is hydrogen or an akyl group having 1 to 4 carbon atoms; and m=1.
 16. The amino acid copolymer according to claim 15 which is prepared by reacting a compound selected from the group consisting of N-methyl lactamine, N-methyl maltamine, lactamine, maltamine, and combinations thereof, with polysuccinimide.
 17. The amino acid copolymer according to claim 1 wherein R₁ is a saccharide moiety having the structure (I); R₅ is hydrogen or is represented by structure I(a); R₆ is hydrogen or is represented by structure I(a) or structure I(b); R₂ is hydrogen or an akyl group having 1 to 4 carbon atoms; and (m+n) is from 2 to
 20. 18. The amino acid copolymer according to claim 17 which is prepared by reacting a compound selected from the group consisting of N-methyl amino corn syrup solids, amino corn syrup solids, N-methyl amino maltodextrin, amino maltodextrin, and combinations thereof, with polysuccinimide.
 19. The amino acid copolymer according to claim 1 wherein the mole percent of (a+b) is from 10 to 50; and the mole percent of (c+d) is from 50 to
 90. 20. The amino acid copolymer according to claim 19 wherein the mole percent of (a+b) is from 15 to 30; and the mole percent of (c+d) is from 70 to
 85. 21. The amino acid copolymer according to claim 1 wherein the sum of (m+n) is from 0 to
 1000. 22. The amino acid copolymer according to claim 21 wherein the sum of (m+n) is from 2 to
 20. 